Wearable exoskeletons are a promising tool for augmenting balance and reducing fall risk. Recent work suggests that active ankle exoskeletons need to act faster than the human to improve reactive balance control. However, the magnitude of exoskeleton torque that is best for improving reactive balance remains unknown. Drawing from the optimal torque for minimizing metabolic expenditure, we hypothesized that reactive balance would improve with increased exoskeleton torque. Participants wearing bilateral ankle exoskeletons were instructed to maintain standing balance during 15cm backward support-surface perturbations. Three exoskeleton plantarflexion torque conditions were tested: NO (Off), LOW (15Nm), or HIGH (30Nm). LOW torque improved balance performance compared to NO torque ( p <0.001), with a 7±3% decrease in peak center of mass (CoM) displacement. Although HIGH torque caused a 9±11% decrease in peak CoM displacement compared to NO torque ( p =0.12), it was not significant due to high intersubject variability. Whereas LOW torque decreased peak CoM displacement in all (range: -0.2 to -1.6cm), HIGH torque only decreased it in some (range = 1.2 to -2.6cm). The change in CoM displacement from LOW to HIGH torque was associated with balance ability, quantified by the narrowing beam test (R 2 =0.29, p=0.06), while this relationship didn't meet conventional statistical significance, likely due to the small sample size, it suggests that higher levels of exoskeleton torque may hinder balance performance in individuals with better balance ability. Taken together, more exoskeleton torque is not always better for balance, highlighting a potential need to personalize exoskeleton torque for balance augmentation.
One third of patients with schizophrenia do not achieve remission with current antipsychotic treatments. Converging data support an immune-mediated component in a subset of cases, overlapping with autoimmune CNS disorders. The B-cell-depleting monoclonal antibody rituximab is used in diseases such as multiple sclerosis and has been explored as an immunomodulatory strategy. We investigated plasma biomarkers, focusing on T-helper-related transcription factors, in relation to outcome after rituximab in schizophrenia. Nineteen severely ill, treatment-resistant patients (n = 9 with schizophrenia and n = 10 with obsessive-compulsive disorder [OCD]) included in an open-label pilot trial, received a single 1000 mg intravenous infusion of rituximab. Symptoms were assessed at baseline and week 12 using PANSS or Y-BOCS, global functioning with PSP, and improvement with CGI-I. Response was defined as "much" or "very much improved" on CGI-I at week 12. For the present analyses, we compared schizophrenia responders with a combined group of schizophrenia and OCD non-responders. Plasma and whole blood were collected at baseline and week 12. Multiplex cytokines and RT-qPCR for the expression of 13 genes coding for cytokines and T-cell-related transcription factors were analyzed, including Th1 and Th17 master regulators TBX21 (T-bet) and RORC (RORγt), respectively. We also constructed a composite rank score combining TBX21 and RORC expression (sum of their within-sample ranks). Six out of eight schizophrenia patients were classified as responders and showed large symptomatic improvement (median PANSS change -70.1) and marked functional gain (median PSP +22.5). Within the analytic sample, schizophrenia responders (n = 6) had higher baseline TBX21 and RORC expression than non-responders (n = 8). Baseline TBX21 correlated with PSP improvement at week 12 (rs = 0.675, p < 0.01). The TBX21+RORC composite rank score showed the strongest association with outcome (higher in responders, p < 0.001; correlated with PSP gain, rs = 0.793, p < 0.001). Classical inflammatory markers, including IL-6, TNF-α and high-sensitivity C-reactive protein, did not differentiate responders. Elevated baseline expression of the Th1- and Th17-associated transcription factors TBX21 and RORC - particularly their combined composite rank score - was associated with symptomatic and functional response to rituximab in treatment-resistant schizophrenia. The data suggest that a TBX21/RORC-defined, Th1/Th17-skewed T-cell signature may characterize a rituximab-responsive immunopsychiatric subtype of schizophrenia, in which B-cell depletion may secondarily modulate pathogenic T-cell response. These findings should be viewed as preliminary and hypothesis-generating for future controlled studies.
The human Y chromosome is among the most structurally dynamic chromosomes in the human genome, yet much of its diversity remains unresolved because of extensive palindromes, ampliconic gene families, satellite-rich heterochromatin and large segmental duplications. What remained unclear was how these diverse forms of variation fit together across the full chromosome, how often similar structures recur in different lineages, and which aspects of organization remain constrained despite rapid sequence turnover. Here, we generated and analyzed 142 nearly complete human Y chromosome assemblies from 17 major haplogroups spanning approximately 180,000 years of evolution, creating a population-scale resource for studying Y chromosome biology and diversity. These assemblies show that structural change on the Y chromosome is recurrent but constrained, even in its most repetitive regions. In the fertility-associated azoospermia factor c (AZFc) region, recurrent inversions, deletions, and complex rearrangements generate a limited repertoire of structural haplotypes. Multicopy ampliconic gene families follow distinct evolutionary paths: DAZ paralogues differ in structural constraint, RBMY evolves within a modular array, and TSPY copy number varies mainly through local expansion and contraction. The centromere and Yq12 heterochromatin vary greatly in size but retain a stable higher-order organization, including a single hypomethylated centromeric core and conserved Yq12 repeat composition and orientation. Methylation across palindromic and ampliconic regions is likewise structured by repeat class, copy order and local architecture. Together, these results provide a population-scale resource for the human Y chromosome and show that its rapid structural evolution is repeatedly funneled into a limited set of architectural outcomes.
Flotation tailings and metallurgical slags from mining often contain toxic Pb, Cd, and Zn. In this study, we evaluated the in situ immobilization of Pb, Cd, and Zn in a Pb-Zn flotation tailing and a smelting slag by adding representative amendments: phosphate-based (ammonium phosphate, phosphoric acid, glassy fertiliser), cementitious (Portland cement), and iron-based (bog iron ore) materials at 1-10% (w/w). Treated samples underwent EPA-TCLP and pH-dependent leaching tests (pH 3-10), with Pb, Cd, and Zn measured by atomic absorption spectroscopy. The untreated tailing leached hazardous Pb (~60 mg/L) and elevated levels of Cd (~0.7 mg/L) and Zn (~53 mg/L), whereas the untreated slag leached negligible metal concentrations. All amendments reduced metal release in a dose-dependent manner. Phosphate amendments were most effective (e.g., 10% H3PO4 cut tailing Pb by 80%, Cd by 60%, and Zn by 30%), while cement and iron additions had much weaker effects. Solid-phase XRD and SEM-EDS analyses indicated the formation of stable calcium-phosphate minerals on sulfide surfaces after phosphate treatment. These findings suggest that low-cost phosphate additives (~5-10%) can substantially immobilize Pb, Cd, and Zn in such wastes. However, under strongly acidic conditions (pH < 3), some remobilization occurred, highlighting the need for further validation. This work provides practical guidance for waste managers on selecting in situ stabilization strategies for Pb-Zn mine wastes.
The construct of borderline personality disorder (BPD) remains contentious, with some arguing that it embraces too much pathology to be of any real value as a clinical diagnosis. Examining BPD's comorbidity is key to understanding its heterogeneous vs. homogeneous nature. This study aimed to uncover differences in patterns of symptoms and their severity between 3 groups of patients a with a DSM-5 diagnosis of BPD: (i) those with a single borderline diagnosis; (ii) those with a dual diagnosis of BPD and antisocial personality disorder (ASPD); those with a dual diagnosis of BPD and narcissistic personality disorder (NPD). Groups were compared in terms of: (i) borderline symptom severity; (ii) self-report measures of emotional dysregulation, suicidality, and identity disturbance; (iii) DSM-defined borderline symptom profiles. Network analysis assessed whether a stable and reproducible structure of symptoms could be seen across all three groups and whether groups differed in symptom prevalence. Results of network analyses showed that the three groups shared the same symptom structure but differed systematically in which symptoms were most strongly endorsed: identity/interpersonal dysfunction in BPD, affective/behavioural dysregulation in BPD+ASPD, and a mixed/intermediate profile in BPD + NPD. BPD+ASPD showed the greatest severity of borderline symptoms, greatest emotional dysregulation, and highest impulsiveness and anger. The BPD group showed the highest identity disturbance and suicidality, BPD + NPD the lowest. In their symptom profiles, BPD were more likely to meet criteria for fear of abandonment, unstable relationships, identity disturbance and suicidality, while BPD+ASPD were more likely to meet criteria for impulsivity, affective instability, and anger control difficulty. The three groups differed on measures of identity and interpersonal relationships, supporting the idea that PD reflects disturbances of relationality. Results highlight that BPD can manifest in different ways that depend on its comorbidity. These differences require treatment to be tailored to the individual patient, with a focus on identity/interpersonal dysfunction when BPD presents alone, and on affective/behavioural dysregulation when BPD co-occurs with ASPD.
Incompetent perforator veins (IPVs) are a critical driver of refractory venous leg ulcers (VLUs). Guideline-endorsed endovenous thermal ablation techniques face substantial implementation barriers due to high device costs and incompatibility with value-based payment models, creating a significant treatment gap. This report introduces Percutaneous Ablation of Perforator Veins using Electrocoagulation (PAPS-PEC)-a novel adaptation of the PAPS principle that leverages ubiquitous electrosurgical equipment to offer a safe, effective, and economically sustainable solution. We present PAPS-PEC application in a 68-year-old male with a recurrent VLU (30×50 mm, CEAP C6) subtended by two IPVs. The office-based procedure was performed under local anesthesia. An 18-gauge electrosurgical needle was guided into each IPV to deliver targeted direct-current energy (10 W, 15 s per quadrant), achieving immediate occlusion confirmed by intraprocedural sonography. The procedure was well-tolerated with no adverse events. Complete ulcer re-epithelialization was achieved at 3 months. At one year, duplex ultrasound confirmed sustained IPV occlusion with no ulcer recurrence. The patient's clinical status improved markedly, with the Venous Clinical Severity Score (VCSS) decreasing from 14 to 4 and the CIVIQ-14 score from 50 to 22. PAPS-PEC is a safe, effective, and exceptionally cost-effective office-based modality for treating IPV-related VLUs. By repurposing existing technology, it directly addresses the economic and accessibility barriers of current standards. These promising findings warrant larger prospective studies to validate its role as a standard-of-care option in managing advanced chronic venous insufficiency, especially in resource-constrained settings. Venous leg ulcers are chronic wounds that heal slowly, often caused by underlying faulty veins known as incompetent perforator veins (IPVs). While standard treatments like laser or radiofrequency ablation are effective, their high cost creates significant barriers for many patients, particularly within healthcare systems that have strict budget controls. This report introduces a new, highly cost-effective technique called Percutaneous Ablation of Perforator Veins using Electrocoagulation (PAPS-PEC). This method utilizes a standard, widely available electrosurgical needle to precisely close these faulty veins. We successfully applied this technique to a 68-year-old man with a non-healing ulcer. The procedure was quick, safe, and performed conveniently in an office setting. His ulcer healed completely, and he remained free of recurrence five years later. PAPS-PEC shows great promise in making advanced vein care both affordable and accessible to a much larger global population, offering a practical and sustainable solution to a common and debilitating health problem.
Closed-set heterogeneous domain adaptation (HDA) for Internet of Things (IoT) intrusion detection aims to transfer detection capabilities across environments that differ in devices, telemetry, feature schemas, attack implementations, label taxonomies, and target supervision availability. Although recent HDA methods report strong performance, their deployment meaning is often unclear because improvements over a weak source-only baseline do not show how much target supervision headroom has been recovered or whether adaptation is preferable to direct target-side labelling under the same budget. This paper presents a controlled, anchor-based benchmark for closed-set HDA in IoT intrusion detection. Edge-IIoTset is used as the main fixed target dataset, with transfer from CICIDS2017, UNSW-NB15, CICIDS2017 + UNSW-NB15, and CICIDS2017 + NSL-KDD under single-source and multi-source settings. The benchmark defines fixed resolved contexts, Intersection and Union representation contracts, a five-class closed-set label contract, leakage-safe preprocessing, and an anchor ladder consisting of source-only, correlation alignment (CORAL), matched-budget target-only, and oracle target-only references. Geometric Graph Alignment (GGA) and the Joint Semantic Transfer Network (JSTN) are evaluated as the primary selected native single-source semi-supervised HDA (SS-HDA) and multi-source semi-supervised HDA (MS-HDA) exemplars, while the Prototype-Matching Graph Network (PMGN) and Conditional Weighting Adversarial Network (CWAN) provide 1:10 method coverage checks. Each method-context-ratio configuration is evaluated across twenty fixed seeds, and DA-versus-target-only differences are tested using paired seed-level statistical evidence. A compact second-target confirmatory experiment using ToN-IoT assesses whether the qualitative headroom recovery and same-budget deployment patterns remain visible under a different IoT/IIoT target. The results show that primary native HDA can recover substantial source-only-to-oracle headroom, but not uniformly. At the 1:10 labelled target ratio, GGA recovers 0.633-0.835 of the available headroom across C1-C4, while JSTN recovers 0.776-0.897 in the contemporary-source MS-HDA family and 0.872-0.926 in the mixed-vintage family. Same-budget comparisons show that DA is deployment-competitive only in some contexts; in others, direct target-side supervised learning is stronger. The benchmark therefore shows that closed-set HDA should be evaluated as target-conditioned, context-resolved evidence rather than as a pooled method leaderboard.
The Sphaerotilus-Leptothrix group of bacteria includes one of the first described microorganisms, Leptothrix ochracea, an uncultured type strain, plus isolates of Leptothrix and Sphaerotilus. This group is unified by the ability to form sheaths and oxidize metals, although L. ochracea exhibits obvious ecological, morphological, and functional differences from the rest of Sphaerotilus-Leptothrix. Recently, there have been calls to combine the group into one genus, Sphaerotilus; however, these studies lacked adequate genomic representation of L. ochracea. Here, we present a comprehensive comparative genomic analysis of the Sphaerotilus-Leptothrix group, including expanded representation of L. ochracea, a closely related novel species, Leptothrix toolikensis, and two new isolates (Leptothrix mechoopdaensis). Analysis of 38 genomes resolves three phylogenetic and functional groups: the ochracea-type Leptothrix (Group 1), the mobilis-type Leptothrix (Group 2), and Sphaerotilus (Group 3). Group 1 genomes form a separate genus based on average nucleotide identity and alignment fraction. The genomes clearly diverge from the rest of Sphaerotilus-Leptothrix in phylogeny, size, and metabolic potential. Group 1 genomes are much smaller (2.59-3.04 Mb) than those of Groups 2 (4.55-6.06 Mb) and 3 (3.94-5.07 Mb), while encoding more metal oxidases and fewer carbohydrate-active enzymes. Group 2 clusters with Group 3 phylogenetically and is similar in organic carbon metabolisms but maintains more metal oxidation genes. Group 2 members lack homogeneity in phenotype and genotype, suggesting that additional isolates and genomes are needed for confident classification. However, Group 1 genomes (L. ochracea and L. toolikensis) show clear divergence, precluding their inclusion in Sphaerotilus and supporting the retention of the genus Leptothrix.IMPORTANCEResearchers have long noted differences in metal oxidation, morphology, and ecology among Sphaerotilus-Leptothrix, but longstanding confusion over phylogeny and genus boundaries led to inconsistent taxonomic classification between the two genera. This confusion stems from previous work that used isolates that are unavailable or lost distinguishing traits in culture, and from limited genomic data. Furthermore, the Leptothrix type strain L. ochracea has never been isolated. This study provides molecular evidence that substantiates calls to reassign some Leptothrix members to the genus Sphaerotilus but adds to an emerging body of evidence that Group 1 L. ochracea and now L. toolikensis represent a functionally distinct lineage. While genomic similarity metrics left taxonomic divisions unclear, integrating metabolic potential with phylogeny resolved genus boundaries based on clear functional groupings. This polyphasic approach for delineating genera clarifies longstanding taxonomic confusion and refines our understanding of functional diversity both across and within Sphaerotilus-Leptothrix lineages.
Coxiella burnetii is the only member of the order Legionellales known to primarily infect vertebrates. The Q fever pathogen is also unusual in that it replicates within an acidified phagolysosome-like vacuole. The evolutionary origins of the virulence determinants underlying this lifestyle remain unclear. More broadly, little is known about how virulence-related traits arise in specialized intracellular lineages, where access to foreign-origin DNA may be more episodic. To address this question, we used Legionellales-wide comparative phylogenomics to reconstruct the gain and loss of traits affecting host interaction, immune evasion, intracellular survival, and metabolism. We found that many virulence-associated traits in C. burnetii predate the modern pathogen and were assembled stepwise in ancestors that likely occupied niches distinct from the acidified vacuolar niche of modern C. burnetii . The common ancestor shared with soft-tick Coxiella endosymbionts likely encoded most C. burnetii type IVB secretion system effectors, indicating that much of the host-manipulation repertoire in C. burnetii was already present before the emergence of the modern pathogen. Distinctive lipopolysaccharide features associated with immune evasion also appear to have accumulated progressively within the Coxiella lineage, including genes implicated in synthesis of virenose, a unique O-antigen sugar critical for C. burnetii virulence. Traits likely to support replication in the acidic Coxiella -containing vacuole likewise accumulated gradually, with generalized stress-tolerance functions predating acquisition of an Mrp cation/proton antiporter that may have further supported pH homeostasis. Additional changes in sugar transport and catabolism, glycolytic control, and respiratory metabolism likely enhanced metabolic flexibility and access to diverse substrates in this nutrient-rich niche. Together, these findings support a model in which vertebrate pathogenicity in C. burnetii emerged through stepwise remodeling of an ancestral host-associated lineage and provide a framework for understanding how virulence-related traits evolve in specialized intracellular pathogens. Coxiella burnetii is the bacterium that causes Q fever, a disease that can spread from animals to humans. Unlike its close relatives, C. burnetii primarily infects vertebrates and grows inside an acidic compartment within host cells. New bacterial pathogens often evolve by gaining genes from other bacteria, but how virulence evolves in lineages that grow only inside host cells, where opportunities to gain new genes may be infrequent, remains unclear. We wanted to understand how C. burnetii evolved the traits needed for its distinctive intracellular lifestyle. By comparing its genome to those of related bacteria across the order Legionellales, we found that features involved in host manipulation, immune evasion, acid tolerance, and nutrient use appeared at different times in its ancestry rather than being acquired all at once by the modern pathogen. Our findings suggest that specialized intracellular pathogens can emerge through gradual changes in ancestral host-associated lineages, including gene acquisition, gene loss, retention of older traits, and repurposing of existing functions.
Nitrogen-containing organic aerosols (NOAs) significantly affect air quality and climate, but their formation mechanisms remain unclear. Here, we investigated the chemical characteristics and light absorption of water-soluble NOA (WSOAN) in PM2.5 from three Sichuan Basin cities of China, Chengdu, Yibin, and Nanchong, during winter 2023, to elucidate both regional consistence and intercity differences of WSOAN formation. Our results showed that the water-soluble organic nitrogen (WSON) of PM2.5 was 0.8-1.0 μg N m-3, and WSOAN accounted for 15.4-38.4% of WSOA. Four WSOAN subclass fragments (amines, amides, amino acids, and imidazoles (IMs)) were identified. The concentration of IMs increased by 1.3-1.4 times during the regional heavy haze event (HHE). Aqueous secondary formation dominated WSOAN production during HHE, contributing 45-58% of total WSON. Chengdu showed a much lower apparent IMs yield than Yibin and Nanchong, mainly due to stronger aerosol acidity and higher levels of dicarbonyls and aerosol liquid water. WSOA light absorption at λ365 nm increased linearly with WSON, with a larger slope in Yibin and Nanchong, indicating a stronger light-absorbing of WSOAN in the two cities. Our study revealed abundant NOA pollution in inland China, which is strongly light-absorbing and largely produced from aerosol aqueous-phase reactions.
When we read, we make predictions about upcoming words; these predictions influence our reading behavior. The success of large language models (LLMs), which, like humans, make predictions about upcoming words, has motivated their use as models of human linguistic prediction. Surprisingly, in the last few years, as LLMs' ability to predict the next word has improved, their ability to explain reading behavior has declined. We argue this is because current LLMs can predict upcoming words much better than human readers can. This 'superhumanness' is driven by LLMs' extensive training data, stronger long-term memory of training examples, and stronger short-term memory. We advocate for LLMs with human-like memory and for new experiments to measure the alignment between humans and LLMs, and we outline directions toward achieving these goals.
This study examines how two competing policy approaches, tobacco-free pharmacies and pharmacy-only tobacco sales, could impact the number of tobacco retailers, retailer availability and neighbourhood disparities in the US. We compiled a list of tobacco retailers in 2023 and coded for primary store type in four US states: California, Connecticut, North Carolina and Ohio. We calculated the reduction in tobacco retailer availability defined as the number of tobacco retailers per 1000 people for each hypothetical policy. We used models fitted for count data and addressed overdispersion and possible spatial dependence to assess associations between the availability of pharmacies in census tracts and neighbourhood characteristics (rurality, age, poverty, race/ethnicity and vacant housing). The hypothetical tobacco-free pharmacy policy showed a much smaller reduction in the number of tobacco retailers (California: 3.9%, Connecticut: 3.1%, North Carolina: 3.0% and Ohio: 4.7%) than a hypothetical pharmacy-only tobacco sales policy (California: 96.1%, Connecticut: 96.9%, North Carolina: 97.0% and Ohio: 95.3%). Regarding the potential impact of each policy on neighbourhood disparities, tobacco-free pharmacies would leave neighbourhood disparities largely unchanged or make them worse in some instances. Pharmacy-only tobacco sales policies would disproportionately locate the few remaining tobacco retailers in neighbourhoods with a greater percentage of people living under the poverty line. Competing pharmacy-based policies about tobacco sales could impact tobacco retailer availability in the US and have different implications for neighbourhood disparities in tobacco retailer availability.
Alcohol-related content in media is overwhelmingly presented positively, and exposure to this content is linked to adolescent drinking. Yet, less is known about how often adolescents encounter alcohol content via media, how exposure varies across platforms, and how adolescents typically engage with such content. We used ecological momentary assessment (EMA) methods to collect detailed, real-time data about alcohol-related content encountered across a variety of digital media sources. High school students recruited through social media (N = 302; mean age = 16.2; 63.9% female sex) completed three 21-day EMA bursts spaced 4 months apart. Participants reported alcohol-related content encountered via scheduled and self-initiated smartphone surveys, yielding 55,352 total reports, including 8792 with alcohol content. We fit multilevel models to evaluate momentary associations between exposure to alcohol content and cognitive outcomes (personal attitudes, perceived peer norms, beliefs that content promotes alcohol use). Nearly all participants (99.3%) reported exposure to alcohol-related content during the monitoring period. The most common sources were Instagram (32.4% of alcohol reports), TikTok (18.1%), and YouTube (7.8%). About one-third of exposures originated from influencers; nearly half of YouTube and Instagram exposures involved industry sources. In-depth engagement (e.g., commenting) with content was rare, although engagement requiring minimal effort ("liking") was endorsed for 25.6% of content reports. Encountering alcohol content on Instagram and Snapchat was associated with personal disapproval of the content; there were few associations with perceived peer norms. Engagement significantly predicted more cognitions favoring alcohol. Adolescents frequently encounter alcohol content across diverse platforms, often from influencers and industry. Much of the content was believed to promote alcohol use. Although behavioral engagement was limited, exposure was linked to attitudes toward content encountered on some platforms. Greater understanding of components and contexts to be targeted for just-in-time interventions delivered in proximity to in vivo exposures can reduce risk for early alcohol engagement.
ConspectusOrbital correlation diagrams are central to chemistry. Based on the symmetry compatibility and orbital overlap amplitude, they link the energy-ordered frontier molecular orbitals (MOs) of reactants and products and have long been a powerful and essential tool for understanding chemical interactions (reactions) and molecular properties. The frontier MOs typically include the highest occupied MOs (HOMOs) and the lowest unoccupied MOs (LUMOs), along with a few nearby orbitals of the reactants. However, it is also known that some reactions cannot be well explained with a few frontier MOs. The main drawback of traditional orbital correlation diagrams is that the orbital energies of the reactants shown in the diagram are calculated assuming they are in free, isolated states. But orbital energy levels can be significantly shifted by external fields and the existence of neighboring molecules. In other words, orbital energy levels can be notably reshuffled when we put reactants "physically" (via electrostatic interactions, Pauli repulsion, and van der Waals interactions) together, even without "chemical" interactions (via orbital mixtures or electron transfers).Here, we introduce a novel concept, "in situ" orbital correlation, and demonstrate its applications. This concept is based on our developed block-localized wave function (BLW), which is the simplest variant of ab initio valence bond (VB) theory. The uniqueness of the BLW method lies in its ability to derive orbital energies of a molecule self-consistently in the presence of other species or external fields, as a BLW solution essentially corresponds to a hypothetical diabatic (or resonance) state, a mathematical construct in which all electron transfers between interacting species are "disabled". In such a way, we can correlate orbitals by considering the field (physical) effects from neighboring species even without any orbital (chemical) interactions.This "in situ" orbital correlation concept was first proposed in the study of the activation mechanism of CO by the diboryne compound B2(NHCR)2, where we demonstrated that when CO approaches B2(NHCR)2, there is a HOMO-LUMO swap in B2(NHCR)2 primarily due to the Pauli repulsion from the carbon lone pair of CO, leading to the compatibility of HOMO and HOMO-1 of B2(NHCR)2 with both π* orbitals of CO. Since then, this concept has been adopted in much of our research. For instance, in our most recent study of NCCL- anions (L = N2, CO, CS), which exhibit notable geometric differences, "in situ" orbital correlation diagrams reveal an orbital swap in the fragment NCC- with the approach of the ligand L and subsequently confirm the C(0) theory proposed by the Frenking group. Previously, we explored the "anti-electrostatic" nature of the Al-Mg bond and confirmed that the bond is purely ionic. This contradicts the view from frontier orbitals of Al(I) and Mg compounds, which exhibit a perfect match for a dative covalent bond between them. Now, with the help of the "in situ" orbital correlation diagram, it becomes obvious that the metal-metal bond is a typical ionic bond, because when the Mg compound is brought close, the energy level of the HOMO of Al(I) compound decreases significantly, leading to a reversal of the HOMO-LUMO energy level order and the extension of the HOMO-LUMO band gap and subsequently minimal probability of any electron transfer. We expect that the novel concept of "in situ" orbital correlation will fundamentally enrich our understanding of chemical reactions, electron transfer pathways, and molecular bonding.
A comparative study was carried out using density functional theory of the adsorption of phenol and p-chlorophenol on two molecular models of biopolymers in aqueous medium: a chitosan dimer and cellobiose. Twelve adsorbent-adsorbate complexes with three initial orientations per system were optimized, and their structural, electronic, and non-covalent properties were analyzed using boundary orbitals, molecular electrostatic potential, NCI/RDG, and QTAIM. In all four systems, the most stable geometry corresponded to the anchoring of the contaminant hydroxyl group to an adsorbent hydroxyl group, identifying O-H···O as the guiding motif of molecular recognition. However, conformational selectivity was strongly dependent on the adsorbent and the aromatic substituent. For phenol, the alternative orientations were 2.7 and 21.2 kcal mol-1 in chitosan and 6.6 and 48.9 kcal mol-1 in cellobiose. For p-chlorophenol, chitosan showed a much more severe discrimination, with penalties of 43.6 and 46.44 kcal mol-1. In contrast, in cellobiose, the alternative orientations remained close to the minimum, with differences of 5.1 and 3.5 kcal mol-1. The effect of Cl was also reflected in the electron topology: PC increased from 3.2 × 10-2 to 6.34 × 10-2 a.u. in chitosan and from 3.2 × 10-2 to 4.2 × 10-2 a.u. in cellobiose, while |V|/G went from 3.6 to 7.5 in chitosan and from 3.00 to 3.1 in cellobiose. Overall, the results show that p-chlorophenol interacts more intensely and selectively with chitosan, whereas cellobiose favors a more flexible, less topologically differentiated adsorption. These results clarify how a para-chloro substituent reorganizes hydrogen-bond-driven adsorption on two biopolymer microenvironments with different functional heterogeneity.
Although much research has been devoted to gait analysis while walking or running, a surprising gap in knowledge is its relationship with upper body function, particularly core stability. The methods used to train and assess athletic locomotion are mainly focused on the lower limbs, while the upper body is often overlooked. Yet, proper body alignment from feet to head is essential for applying maximum force to the ground, thereby moving faster and more efficiently. It is believed that the core, which connects the upper and lower body, should be strong. The training of many athletes is therefore aimed at developing core muscle strength. However, for most of them, rigid core musculature associated with reduced spinal mobility may not be beneficial. Instead, core strength should be developed to the extent that allows race walkers and runners to optimize their performance. Accordingly, methods reflecting the functional nature of core strength, along with measures of postural alignment and lateral lumbopelvic stability, should be used to assess training effectiveness. To this end, a comprehensive head-to-toe approach to the assessment of athletic locomotion is recommended. Special emphasis should be placed on the role of postural and core stability in walking and running gait.
Water contaminated by textile dyes is a tremendous risk to human health and the environment due to its toxic and carcinogenic nature, thus requiring advanced and efficient removal strategies. Therefore, this study aimed to investigate the photo-oxidation performance of few- and multi-layer Ti3C2Tx nanosheets (MXenes) decorated with TiO2 nanoparticles for methyl orange removal from synthetic solutions. The quantification of photogenerated hydroxyl radicals by fluorescence revealed much higher OH• production for TiO2-decorated samples, especially for multi-layer MXene, in which it was 2.8 times higher than that of few-layer MXene. However, photocatalysis was morphology-controlled: despite lower OH•, the few-layer MXene achieved the highest dye conversion (~45% after 5 h), attributed to shorter charge migration distances and more accessible TiO2 active sites, enabling effective h+ and superoxide-driven pathways. Moreover, the detected -OH surface terminations verified on MXenes promoted a notable adsorption capacity, especially for the multi-layer samples (~31%) via interlayer trapping and H-bonding. Therefore, our results demonstrate that few-layer MXenes are promising candidates for the efficient removal of methyl orange and highlight the potential of TiO2-decorated MXenes as promising photocatalysts for environmental remediation.
Abnormal uterine bleeding is the most common symptom of endometrial cancer, but due to the low prevalence of underlying malignancy (3%), clinicians must distinguish those who can be quickly reassured from those who require urgent diagnosis and cancer treatment. The current diagnostic pathway is limited by the low specificity of transvaginal ultrasound, which leads to large numbers of invasive follow-up tests (hysteroscopy and biopsy). Transvaginal ultrasound may also miss almost a quarter of serous cancers, which have the poorest prognoses, and overall performance of this test, particularly specificity, is much lower in Black women. Many approaches have been explored to develop simple, objective, molecular triage tests, of which quantitative polymerase chain reaction-based DNA methylation tests in cervicovaginal samples have made significant progress. These data call on clinicians, researchers, and policymakers to invest in innovative diagnostic solutions and to reshape the diagnostic landscape for a cancer whose incidence and mortality continue to rise.
Women's economic empowerment is a key development goal; yet, significant gender inequalities in employment, income, and economic decision-making persist in low- and middle-income countries, particularly in sub-Saharan Africa. Even with economic growth, women are often stuck in informal and precarious jobs, facing structural barriers related to labor markets, access to finance, asset ownership, and restrictive legal frameworks. Most existing research on Women's economic empowerment has focused on micro-level interventions, such as financial support, training, and mentorship, providing limited insights into the impact of macro-level and structural policies. New research suggests that macroeconomic, fiscal, and labor market policies are not gender-neutral; they can shape employment opportunities and income security differently, particularly in contexts with unequal unpaid care responsibilities. However, evidence on macro-level, gender-responsive policies and their effects on women's economic empowerment remains scattered across various policy areas and outcomes in sub-Saharan Africa. This Evidence and Gap Map systematically identifies, categorizes, and maps the existing evidence to facilitate informed policy-making, prioritize research, and guide future synthesis. To map evidence on gender-responsive macro-level policies and their impact on women's economic empowerment in sub-Saharan Africa. From January to September 2024, we searched the following databases, limiting our results to English language publications: CAB Abstracts, Web of Science, Dimensions, and Scopus. We also utilized gray literature sources, including organizational databases, Google Scholar, and registries. Two reviewers independently screened the titles, abstracts, and full texts of potentially eligible articles to determine their inclusion based on the specified eligibility criteria. Studies were included if they focused on populations in sub-Saharan Africa, examined macro-level gender-responsive policies, reported outcomes related to women's economic empowerment, and utilized either primary or systematic or scoping review study designs. We developed and pilot-tested a data extraction code set in EPPI-Reviewer, where data were extracted and coded in duplicate. To evaluate the quality of the reviews, we employed the AMSTAR2 tool; however, we did not assess the quality of the primary studies. This Evidence and Gap Map includes a total of 245 articles made up of 224 primary studies and 21 systematic and scoping reviews that evaluate the impact of gender-responsive macro-level policies on women's economic empowerment. The majority of the studies focused on social protection and informal economy policy interventions, with women's economic opportunities and well-being being the most frequently examined outcomes. Most of the research was conducted in South Africa (about 17% of the included studies) Significant gaps were identified in advocacy interventions for women's economic empowerment, as well as in the exploration of women's agency as an outcome related to their economic empowerment. Additionally, most of the evidence is based on non-experimental and qualitative study designs, indicating a substantial gap for future research. The systematic reviews incorporated in this EGM are predominantly of moderate quality, with less than 30% categorized as high quality. The Evidence and Gap Map reveals a substantial yet uneven body of evidence regarding women's economic empowerment interventions in sub-Saharan African countries. The evidence is most concentrated around social protection policies and interventions in the informal economy, with strong coverage of outcomes related to women's economic opportunities and well-being. These areas are comparatively well-researched and provide opportunities for further evidence synthesis to guide policy and program design. In contrast, there is limited evidence on agency-related outcomes and implementation processes, which hampers understanding of how and why interventions foster empowerment. Additionally, macroeconomic policies and women's economic empowerment advocacy interventions are underrepresented, despite their importance in addressing structural barriers to women's economic participation. Methodologically, the evidence base is primarily composed of non-experimental and summative evaluations, with fewer studies using rigorous designs that can identify causal effects or track long-term empowerment trajectories. Overall, the map highlights both well-established evidence clusters and significant gaps, especially concerning structural interventions, empowerment processes, and methodological diversity. The Evidence and Gap Map (EGM) on gender-responsive macro-level policies and women’s economic empowerment revealed studies that were disproportionately concentrated in sub-Saharan African countries. Additionally, the existing reviews were generally of moderate quality. The EGM in brief This EGM examines and discusses the evidence on macro-level policy interventions that are gender-responsive and designed to promote women’s economic empowerment. It emphasizes that much of the existing evidence centers on social protection policies, particularly childcare policies, and their impact on physical well-being outcomes. Most of this evidence comes from Southern Africa. What Is this EGM about? Women in low- and middle-income countries (LMICs), particularly in sub-Saharan Africa, are often confined to informal and low-quality jobs because of structural, legal, and macroeconomic barriers that cannot be overcome by economic growth alone. This intervention aims to tackle these constraints by synthesizing evidence on gender-responsive macro-level policies that foster inclusive labor markets and promote sustainable economic empowerment for women. What Is the aim of this EGM? To provide evidence from studies on macro-level policy interventions that are gender-responsive and aimed at promoting women’s economic empowerment in sub-Saharan Africa. What studies are included? The EGM included 245 studies, consisting of 224 primary studies and 21 review studies, all evaluating macro-level policy interventions designed to promote women’s economic empowerment. These studies specifically targeted gender-responsive interventions in sub-Saharan Africa. What Are the main findings of this Gap Map? The evidence presented in this EGM underscores the importance of macroeconomic and social protection policies in promoting women’s economic empowerment. Specifically, it highlights clusters of evidence related to fiscal, childcare, and healthcare policies. Additionally, there is significant evidence concerning decent work and unpaid care work policies within the informal economy. Most of the evidence is drawn from Southern African countries, including South Africa, Malawi, Zambia, and Zimbabwe. The systematic reviews included in this EGM are primarily of moderate quality, with fewer than 30% classified as high quality. Over 45% of the studies reported outcomes related to well-being. Furthermore, there were 29 studies evaluating policy interventions on women’s employment opportunities and 48 studies focusing on income-related interventions. While all regions of sub-Saharan Africa were represented, the majority of studies originated from Southern Africa (37%), with only a small percentage coming from Central Africa (2.7%). Most interventions in Eastern and Western Africa concentrated on social protection policies, with fewer studies addressing advocacy initiatives for women’s economic empowerment. What do the Findings of the Map Mean? This EGM aims to identify gender-responsive macro-level policy interventions that promote women’s economic empowerment. The EGM is limited by uneven evidence across geographies, and it is overrepresented in terms of interventions related to social protection and macroeconomic interventions compared to other interventions, such as advocacy. Evidence is more represented in Southern Africa. , with a notable number of studies also available from Western and Eastern Africa. This map helps establish an evidence base in the field, allowing funders and researchers to identify existing gaps and prioritize future research efforts. How up-to-date is this EGM? We conducted a search for relevant studies up to September 25, 2024.